MONOMERS FOR THERMOSETTING OR ADHESIVE EPOXY RESINS

Abstract

The present invention relates to epoxy precursors, their preparation process and their use as monomers for the development of thermosetting resins or associated adhesives.

Description

Title of the invention: Monomers for thermosetting or adhesive epoxy resins FIELD OF INVENTION

[0001] The field of the present invention is that of the synthesis of epoxy precursors and their use as monomers for the production of thermosetting resins or associated adhesives. More specifically, the present invention relates to the use of polyfunctional phenolic aromatic compounds derived from renewable resources, and not from petroleum, natural gas, coal, or other fossil resources, exhibiting improved environmental and safety properties (HSE properties) and leading to thermosetting resins that do not exhibit performance degradation in use, and whose end-of-life management can be facilitated. STATE OF THE ART

[0002] Nowadays, among polyfunctional phenolic aromatic compounds, one can cite in particular bisphenol A diglycidyl ether (DGEBA or BADGE), manufactured from bisphenol A (BPA) and epichlorohydrin (ECH). These two precursors are classified as Carcinogenic, Mutagenic, and Reprotoxic (CMR), namely category 2 reprotoxicant and endocrine disruptor for BPA and category IB carcinogen for ECH.

[0003] In recent years, several solutions have been implemented to develop compounds with a low environmental footprint and reduce their toxicity. For example, in 2007, Solvay presented the EPICEROL® process for the bio-based production of hydroxyethyl starch (HES) from glycerol. BPA, on the other hand, can be obtained by reacting phenol obtained by distilling forestry industry waste with acetone produced by fermentation (SuperSap® prepolymer from Entropy Resins).

[0004] However, the use of bio-based and renewable BPA and ECH does not change the hazardous nature of these substances, which remain classified as CMR regardless of their origin. Therefore, it is preferable to improve their properties with new, less polluting and non-toxic precursors for humans rather than implementing a "drop-in" product-for-product substitution that would retain the potential hazards of the products used.

[0005] Furthermore, in certain uses such as, for example, food contact (coatings for metal containers, tanks, etc.) or the rehabilitation of water pipes The potential leaching of epichlorohydrin, chlorinated residues contained in DGEBA-based thermosetting materials, and BPA from the degradation of DGEBA-based thermosetting materials is a concern for public authorities. (Rajarsarkka et al. Water Res. 2016,103, 133-140; Cantoni et al. Sci. Total Environ. 2021, 783, 146908; Lipke et al. Eur. J. Pharm. Biopharm. 2016,101, 1-8). TECHNICAL PROBLEM

[0006] The technical problem that the present invention aims to solve is therefore to obtain new polyfunctional epoxidized aromatic phenolic compounds from renewable resources that exhibit improved HSE properties. Description of the invention

[0007] Thus, a first object of the invention is a compound of formula (I) in which: - Ri and R3 are identical and denote a group according to the following formula (II): in which: - E represents a single bond or a divalent hydrocarbon group in CrCi2 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); - R5 represents a group of formula (II) identical to Ri and R3 or -O-X4, with X4 representing a Ci-Ci8 alkyl, a C2-Ci8 alkenyl, a C6-C14 aryl or a (C6-Ci4)aryl-(Ci-C6)alkyl, preferably R5 represents a group of formula (II) identical to Ri and R3; - R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl group in CrC24.

[0008] A second object of the invention is a process for preparing a compound of formula (I) according to the invention, comprising a step b) of epoxidation of a compound of formula (1-2) in which: - Ri” and R3” are identical and designate a group according to the following formula (II-2): X2 (U-2) in which: - E represents a single bond or a divalent hydrocarbon group in Ci-Ci2 possibly comprising one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of the group of formula (II-2) to the rest of the compound of formula (1-2); - R5' ' designates a group identical to Ri” and R3' ', or -O-X4, with X4 representing a Ci-Ci8 alkyl, a C2-Ci8 alkenyl, a C6-CM aryl or a (C6-Ci4)aryl-(Ci-C6)alkyl; - R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl in CrC24, preferably a hydrogen atom or an alkyl in CrCi2, preferably a hydrogen atom or an alkyl in CrC4, preferably a hydrogen atom or an alkyl in Ci-C6, more preferably a hydrogen atom.

[0009] A third object of the invention is a use of a compound of formula (I) according to the invention as a precursor of polymer materials, in particular of thermosetting materials, or as an adhesive.

[0010] A fourth object of the invention is a process for preparing a thermosetting material comprising a polymerization step of a compound of formula (I) according to the invention, optionally the process further comprises a crosslinking step.

[0011] A fifth object of the invention is a thermosetting material that can be obtained by the process according to the fourth object. DEFINITIONS

[0012] In the present, unless expressly stated otherwise, all percentages (%) indicated are percentages (%) in moles.

[0013] Any interval of values ​​designated by the expression "between a and b" as well as by the expression "from a to b" means the domain of values ​​going from a to b (that is to say including the strict bounds a and b).

[0014] For the purposes of the present invention, "hydrocarbon chain" means a chain comprising one or more carbon atoms and one or more hydrogen atoms.

[0015] For the purposes of this invention, the term "Cx-Cy alkyl group" refers to a monovalent, saturated, linear or branched hydrocarbon chain comprising x to y carbon atoms, where x and y are integers. Examples of Ci-C6 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, neopentyl, and hexyl, preferably methyl, ethyl, propyl, or isopropyl. For example, CrCi2 alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. For example, Ci-C4 alkyl groups include... cite the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, or tert-butyl groups.

[0016] The expression "C-Cj aryl" designates an aromatic hydrocarbon group comprising from i to j carbon atoms, i and j being integers. This group may comprise one or more fused rings. Advantageously, it is phenyl.

[0017] For the purposes of this invention, a "Cx-Cy carbocycle" is defined as a saturated or instanominated non-aromatic cyclic hydrocarbon group comprising x to y carbon atoms. A carbocycle may be monocyclic or polycyclic. When the carbocycle is polycyclic, it comprises at least two, advantageously two or three, fused, bridged, or spiral rings. For example, it may be a saturated carbocycle, particularly at C3-C8. Examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. It may also be an unsaturated carbocycle, that is, one comprising at least one carbon-carbon double or triple bond, particularly at C3-C8. Examples include the groups cyclopropene, cyclobutene, cyclopentene, cyclohexene, 1,4-cyclohexadiene, cycloheptene, cycloheptyne, cyclooctene, and cyclooctyne.

[0018] For the purposes of this invention, the term "Cx-Cy alkenyl group" refers to a monovalent, linear or branched hydrocarbon chain comprising at least one double bond and x to y carbon atoms. Examples include ethenyl, propenyl, allyl, butenyl, pentenyl, and preferably allyl hexenyl groups.

[0019] By "heteroatom", we mean any atom other than carbon or hydrogen such as, for example, sulfur, nitrogen or oxygen atoms.

[0020] For the purposes of this invention, "halogen atom" or "halogen" means fluorine, chlorine, bromine, and iodine atoms. For the purposes of this invention, "stereoisomer" means a configurational isomer, and in particular a geometric or optical isomer.

[0021] Geometric isomers result from the different position of the substituents on a double bond which can then have a Z or E configuration.

[0022] Optical isomers result, in particular, from the different spatial positions of substituents on a carbon atom containing four different substituents. This carbon atom then constitutes a chiral or asymmetric center. Optical isomers include diastereomers and enantiomers. Optical isomers that are mirror images of each other but not superimposable are designated as "enantiomers." Optical isomers that are not mirror images of each other are designated as "diastereomers." A mixture containing equal amounts of two individual enantiomeric forms of opposite chirality is designated as a "racemic mixture".

[0023] According to the present invention, the disclosed compounds encompass all stereoisomers of said compounds.

[0024] For the purposes of this invention, "ambient temperature" means a temperature generally ranging from 15°C to 40°C, preferably from 20°C to 30°C, in particular around 25°C.

[0025] The compounds mentioned in the description may be of fossil origin or bio-based. In the latter case, they may be partially or totally derived from biomass or obtained from renewable raw materials derived from biomass. Similarly, the compounds mentioned may also come from the recycling of materials already used, that is to say, they may be partially or totally derived from a recycling process, or obtained from raw materials themselves derived from a recycling process.

[0026] In this description, "approximately" means that the value in question may be 10% lower or higher, in particular 5%, and in particular 1% higher, than the value indicated. DETAILED DESCRIPTION OF THE INVENTION

[0027] In the sense of the present invention, the various embodiments presented in the description as a whole can be used alone or in combination with each other, without limitation of combination. Compound of formula (I)

[0028] The object of the present invention relates to a compound of formula (I): Ri 5 T ^3 o in which: - Ri and R3 are identical and denote a group according to the following formula (II): in which: - E represents a single bond or a divalent hydrocarbon group in CrCi2 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); - R5 represents a group of formula (II) identical to Ri and R3 or -O-X4, with X4 representing a CrCi8 alkyl, a C2-Ci8 alkenyl, a C6-Ci4 aryl or a (C6-Ci4)aryl-(Ci-C6)alkyl, preferably R5 represents a group of formula (II) identical to Ri and R3; - R2, R, and R6, whether identical or different, represent a hydrogen atom or an alkyl group in CrC24.

[0029] Advantageously, R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl group in the form of Ci-Ci2, preferably in Ci-C6, and even more preferably in CrC4. Preferably, R2, R4 and R6 represent a hydrogen atom.

[0030] E may represent a divalent hydrocarbon group in CrCi2, in particular in Ci-Cio, optionally comprising one or more heteroatoms, in particular an alkyl group in CrCi2, in particular in CrCio, optionally comprising one or more heteroatoms. When present, the heteroatoms are preferably chosen from S, O, and N, in particular from O and N, preferably O. Preferably, E does not comprise any heteroatom.

[0031] E may represent a divalent hydrocarbon group in CrC4, typically at C2, or in C5-C10, typically at C8, optionally comprising one or more heteroatoms. E may represent an alkyl group in CrC4, typically at C2, or in C5-C10, typically at C8, optionally comprising one or more heteroatoms. When present, the heteroatoms are preferably selected from S, O, and N, in particular from O and N, preferably O. Preferably, E does not comprise any heteroatoms.

[0032] E can represent -(CH2)n- with n an integer equal to 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0033] E can advantageously represent a single bond or an alkyl in C1-C12, in particular in Ci-Cio.

[0034] Xi, X2 and X3, identical or different, may represent a hydrogen atom or a Ci-C6 alkyl group. Advantageously, X2 and X3 each represent a hydrogen atom. Advantageously, Xi represents a hydrogen atom or a Ci-C6 alkyl group, such as a methyl group.

[0035] Advantageously, Xb X2 and X3, whether identical or different, represent a hydrogen atom or a Ci-C6 alkyl group, preferably a hydrogen atom or a methyl group, and / or Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4-C8 carbocycle, preferably a saturated C4-C8 carbocycle, advantageously a cyclopentane, a cyclohexane or a cycloheptane.

[0036] When E represents a single bond, then Xb, X2, and X3, whether identical or different, preferably represent a hydrogen atom or a C1-C6 alkyl group, more preferably a hydrogen atom or a methyl group. Advantageously, at least one of Xi, X2, and X3, preferably Xb, represents a C1-C6 alkyl group, more advantageously a methyl group.

[0037] When E represents a divalent hydrocarbon group in CrCi2 possibly comprising one or more heteroatoms, then Xb X2 and X3, identical or different, preferably represent a hydrogen atom or an alkyl in Ci-C6, preferably a hydrogen atom or a methyl, more preferably a hydrogen atom, and / or Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links, preferably a C4 to C8 carbocycle.

[0038] When Xi and X3 or X2, or a carbon atom of the divalent hydrocarbon group of E and X3 or X2 are bonded together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links, the C4 to C8 carbocycle or the heterocycle having 5 to 8 links is advantageously saturated, and preferably is a cyclopentane, a cyclohexane or a cycloheptane, more preferably a cyclohexane.

[0039] Advantageously, X4 represents a CrCi2 alkyl, an allyl, a phenyl or (C6)aryl-(Ci-C6)alkyl, preferably a Ci-C6 alkyl, an allyl, a phenyl or a benzyl, preferably a CrC4 alkyl, more preferably a methyl or an ethyl.

[0040]

[0041] Advantageously, the compound according to the invention is a compound of formula (I) in which: - Rb, R3 and R5 of formula (I) are identical and denote a group according to formula (II) in which: - E represents a single bond or a C1-C12 alkyl possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom or an alkyl group in the Ci-C6 configuration, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 saturated carbocycle; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); - R2, R4 and R6, whether identical or different, represent a hydrogen atom or an alkyl in Ci-Ci2, preferably R2, R4 and R6 represent a hydrogen atom. Even more advantageously, the compound of formula (I) is chosen from the group (HAS) (D) , and their mixtures.

[0042] Process for preparing a compound of formula (I)

[0043] According to a first embodiment, the compound of formula (I) can be prepared By a process comprising an epoxidation step of a compound of formula (I-2) defined below, this step thus makes it possible to obtain a compound of formula (I). This epoxidation step is preferably preceded by an esterification step allowing the ester functions of the groups of formula (II) to be obtained, it makes it possible to obtain the compound of formula (1-2).

[0044] The preparation process described below is suitable for preparing all kinds of compounds of formula (I). For example, this preparation process makes it possible to prepare compounds of formula (I) both when R5 represents -O-X4 and when R5 represents a group of formula (II) identical to Ri and R3).

[0045] The compound of formula (I) can be prepared in two steps from the compound of formula (1-1): R4 (M) in which: - Ri' and R3' denote an -OH group, - R5' designates a -OH or -O-X4 group, with X4 identical to that of the formula (I), and - R2, R4 and R6 are identical to those of formula (I).

[0046] The compound of formula (11) is preferably phloroglucinol or a compound of formula (1-1) in which R5' denotes -O-X4, with X4 identical to that of formula (1).

[0047] The first step a) is a step of bringing the compound of formula (1-1) into contact with a compound according to the following formula (II-1): (11-1) in which: Y represents a group -OH, -ORa, halogen, with R, representing a Ci-C6 alkyl group, and - E, Xi, X2 and X3 are as defined previously.

[0048] When Y represents a halogen atom, it preferably represents a chlorine atom. Preferably, Y represents an -OH group.

[0049] The conditions of this esterification step a) are a transposition of the usual conditions for esterification or transesterification reactions, for example, the conditions for Steglich esterification in the presence of dicyclohexylcarbodiimide (DCC) or A4(3-dimethylaminopropyl)-IV-ethylcarbodiimide (EDC) as a coupling agent and 4-dimethylaminopyridine (DMAP) as a catalyst. This reaction can be carried out in an organic solvent, preferably polar and aprotic, such as tetrahydrofuran, and preferably at a temperature ranging from 0 to 40 °C. The reaction time can range from 1 to 30 hours.

[0050] When R5' designates a -OH group, step a) can be carried out with a compound molar ratio of formula (Il):compound according to formula (Il-l) ranging from 2.9 to 5, preferably from 3.1 to 4, typically about 3.6.

[0051] When R5' designates -O-X4, step a) can be carried out with a compound molar ratio of formula (Il):compound according to formula (II-l) ranging from 1.9 to 5, preferably ranging from 2 to 4, typically ranging from 2.1 to 2.4.

[0052] Step a) can therefore be represented by the following diagram. (1-2)

[0053] Step a) therefore leads to obtaining a compound of formula (1-2) in which: - Ri” and R3” are identical and designate a group according to the following formula (II-2): X2 (11-2) in which: - E, Xi, X2 and X3 are as defined previously; - the symbol (*) represents the attachment point of the group of formula (II-2) to the remainder of the compound of formula (1-2); - R5' ' designates a group identical to Ri” and R3' ', or -O-X4, with X4 identical to that of formula (I), - R2, R4 and R6 are identical to those of formula (I).

[0054] R5” advantageously designates a group identical to Ri” and R3”.

[0055] Step b), which is the second step when step a) is carried out, is a step of contacting the compound of formula (1-2) as defined above with an epoxidizing agent. In the context of the present invention, the epoxidizing agent is a compound or a mixture of compounds that allows the transformation of the C=C double bond of the compound of formula (1-2) into an epoxide function. This step therefore leads to obtaining a compound of formula (I) as defined above.

[0056] Epoxidizing agents are numerous and well known to those skilled in the art. For example, metachloroperbenzoic acid (MCPBA) is an epoxidizing agent. The conditions of this epoxidation step b) are a transposition of the usual conditions for epoxidation reactions. This reaction can be carried out in an organic solvent, preferably polar and aprotic, such as dichloromethane, and preferably at room temperature. The reaction time can range from 1 hour to 50 hours.

[0057] In a second embodiment, the process for preparing a compound of formula (I) according to the invention comprises a step d) of bringing the following compounds into contact: - a compound of formula (1-1) as defined previously;

[0058] - a compound of the following (III-l) formula: X in which: y2- e xt X3 Xi O - Y2 represents a function capable of reacting with an -OH group to form an ester bond, and - E, Xb X2 and X3 are identical to those of formula (II).

[0059] Y2 advantageously represents a group -C(O)-Y, with Y as defined previously.

[0060] In this embodiment, when R5' designates a -O-X4 group, the compound of formula (1-1) can be prepared by an ether bond formation reaction to obtain the substituent R5 from a compound of formula (1-0) which corresponds to the compound of formula (11) in which R5' is replaced by an -OH group.

[0061] Thus, according to this embodiment, the compound of formula (I) can be prepared by a preparation process comprising two successive reactions: a first of ether bond formation and a second of ester bond formation.

[0062] The compound of formula (I) can therefore be prepared in two steps from the compound of formula (1-0). The compound of formula (10) is preferably phloroglucinol.

[0063] The first step c) is a step of contacting the compound of formula (1-0) with a compound YrX4 in which - Yi represents a function capable of reacting with an -OH group for to form an etheric bond, and - X4 is as defined previously.

[0064] The Yi functions are well known to those skilled in the art. For example, Yi can represent an -OH group or a halogen atom, the halogen preferably being a bromine or chlorine atom. Preferably, Yi represents an -OH group.

[0065] The conditions of this step c) are a transposition of the usual conditions for ether bond formation reactions. This reaction can be carried out in an organic solvent, for example a polar and aprotic solvent such as tetrahydrofuran, or a nonpolar solvent such as toluene.

[0066] When Yi represents an -OH group, the compound YrX4 can also act as the solvent for the reaction, particularly when X4 represents a Ci-Ci8 alkyl group. Advantageously, when X4 represents a Ci-C6 alkyl group, YrX4 acts as the solvent, preferably when X4 represents a CrC4 alkyl group, and more preferably a methyl or ethyl group. YrX4 is therefore preferentially methanol or ethanol.

[0067] The reaction can be carried out under acidic conditions, for example in the presence of a strong Brønsted acid such as sulfuric acid and preferably at a temperature ranging from 0 to 90 °C, preferably from 20 °C to 70 °C, typically around 50 °C. The reaction time can range from 1 hour to 40 hours.

[0068] Step d), which is the second step when step c) is implemented, is a step of contacting the compound of formula (1-1) as defined above with a compound of formula (III-1) as follows: as defined previously.

[0069] This step therefore leads to obtaining a compound of formula (I) according to the invention.

[0070] The conditions of this step d) are such as defined for step a).

[0071] The compound (I) thus obtained can be separated from the reaction medium by methods well known to those skilled in the art, such as, for example, by extraction, evaporation of the solvent, or by precipitation and filtration. The same applies to the compound of formula (1-2) obtained at the end of step a) or to the compound of formula (II) obtained at the end of step c) when it is carried out.

[0072] The compounds can also be purified if necessary by techniques well known to those skilled in the art, such as by recrystallization if the compound is crystalline, by distillation, by silica gel column chromatography or by high-performance liquid chromatography (HPLC).

[0073] Use of a compound of formula (I) and process for preparing thermosetting materials

[0074] Compounds of formula (I) are particularly interesting precursors for the preparation of polymeric materials, and in particular thermosetting polymeric materials. A thermosetting material is a polymeric material obtained by a polymerization step that renders the material irreversibly rigid. This hardening is due to extensive cross-linking between the polymer chains.

[0075] Crosslinking is a chemical reaction that creates covalent chemical bonds between polymer chains that are not initially covalently linked. This reaction is generally initiated by heat, pressure, changes in pH, or radiation, and most often requires a crosslinking agent. The crosslinking of linear or branched polymer chains is accompanied by an increase in the molecular dimensions of the chains, particularly their molar masses, and leads to the formation of a network of crosslinked polymers.

[0076] Thermosetting polymers have very good mechanical properties, in particular strength, and can also be used as an adhesive.

[0077] Thus, another object of the invention relates to the use of a compound of formula (I) for the preparation of a thermosetting material. Also, another object of the invention relates to a process for preparing a thermosetting material comprising a polymerization step of a compound of formula (I).

[0078] This polymerization can be carried out with at least one monomer M different from the compound of formula (I). This monomer M has at least two reactive functional groups that can react with the epoxide functional groups present in the compound of formula (I). These functional groups are well known to those skilled in the art. For example, amine, amide, carboxylic acid and derivative functional groups such as acid anhydrides, and phenols may be mentioned.

[0079] The monomer M can preferably be chosen from among diamines such as urea and its derivatives or aliphatic diamines with a cyclohexyl center such as those marketed under the name Priamine 1071 or Priamine 1075.

[0080] The monomer M can be chosen from acid anhydrides, aromatic amines, cycloaliphatic amines, primary aliphatic amines and carboxylic acids.

[0081] The following acid anhydrides may be cited: hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, chlorendic anhydride, nadic anhydride, tetrachlorophthalic anhydride, pyromellitic dianhydride, 1,2,3,4 cyclopentanetetracarboxylic acid dianhydride, glutaric anhydride, phthalic anhydride, and aliphatic acid polyanhydrides such as polyazelaic polyanhydride or polysebatic polyanhydride.

[0082] The following aromatic amines may be cited: 4,4'-aminodiphenylsulfone, also called DDS; 4,4'-methylene-bis(2,6-diethylaniline); 4,4'-(phenylenediisopropyl)-bis(2,6-dipropylaniline); 4,4'-methylene-bis(2-isopropyl-6-methylaniline), also called M-MIPA; 4,4'-methylene-bis(2,6-diethylaniline), also called M-DEA; 4,4'-methylene-bis(3-chloro-2,6-diethylaniline), also called M-CDEA; 4,4'-(phenylenediisopropyl)-bis(2,6-dimethylaniline); 4,4'-(phenylenediisopropyl)-bis(2,6-diethylaniline); 4,4'-(phenylene-diisopropyl)-bis(2,6- dipropylaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-düsopropylaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-dimethyl-3-chloroaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-diethyl-3-chloroaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-dipropyl-3-chloroaniline), 4,4'-(phenylenediisopropyl)-bis(2,6-diisopropyl-3-chloroaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-dimethylaniline), 3,3'-(phenylenediisopropyl)-bis(2,6-diethylaniline), 3,3'-(phenylene-diisopropyl)-bis(2,6-dipropyl-aniline), 3,3'-(phenylene-diisopropyl)-bis(2,6-dimethyl-3-chloro-aniline), 3,3'-(phenylene-diisopropyl)-bis(2,6-diethyl-3-chloro-aniline), 3,3'-(phenylene-diisopropyl)-bis(2,6-dipropyl-3-chloro-aniline), 3,3'-(phenylene-diisopropyl)-bis(2,6-diisopropyl-aniline) and 3,3'-(phenylene-diisopropyl)-bis(2,6-düsopropyl-3-chloro-aniline).

[0083] The following cycloaliphatic amines may be cited: 1,3-cyclohexanediamine, l,4-cyclohexanediamine, l,3-bis(aminomethyl)cyclohexane, l,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 4,4'-diamino dicyclohexylmethane also called PACM, 3,3'-dimethyl-4,4'-dicyclohexylmethane also called MACM, isophorone diamine also called IPDA, and menthane diamine.

[0084] Primary aliphatic amines may be cited: ethylenediamine, diethylenetriamine, triethylenetetramine, piperazinoethylethylenediamine, aminoethyldiaminoethylpiperazine, aminoethylpiperazinoethylethylenediamine, aminoethylpiperazine, aminoethylethanolamine (AEEA marketed by Dow Chemical), polyetheramine-type amino monomers prepared from ethylene oxide, propylene oxide, or ethylene oxide / propylene oxide mixtures (such as the Jeffamines series marketed by Huntsman), 4,7,10-trioxatridecan-1,13-diamine, polytetrahydrofuranamine (marketed by BASF), polyamidoamines, polyaminoimidazolines, unbranched or hyperbranched polyethyleneimines (PEI), and polyalkyleneamines.

[0085] The following carboxylic acids may be cited: carboxylic acids comprising 2 to 40 carbon atoms, such as linear diacids (glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic and their higher mass homologues) as well as their mixtures, or fatty acid derivatives, trimers (oligomers of 3 identical or different monomers) and mixtures of fatty acid dimers and trimers, in particular of vegetable origin. These compounds result from the oligomerization of unsaturated fatty acids such as: undecylenic, myristoleic, palmitoleic, oleic, linoleic, linolenic, ricinoleic, eicosenoic, and docosenoic acids, which are commonly found in pine, rapeseed, corn, sunflower, soybean, grapeseed, flaxseed, and jojoba oils, as well as eicosapentaenoic and docosahexaenoic acids, which are found in oils of fish. We can also mention aromatic carboxylic acids comprising 2 to 40 carbon atoms, such as aromatic diacids like phthalic acid, trimellitic acid, terephthalic acid or naphthalenedicarboxylic acid.

[0086] This polymerization step of a compound of formula (I) can lead directly to a thermosetting material or it can lead to obtaining a mainly linear polymer chain which will subsequently have to undergo an additional crosslinking step in order to obtain the thermosetting sand material.

[0087] When the compound of formula (I) is divalent, that is, when this compound has two groups of formula (II) and therefore two epoxide functions, then the preparation process preferably includes an additional crosslinking step with a crosslinking agent, also called a curing agent. When the compound of formula (I) is trivalent, that is, when this compound has three groups of formula (II) and therefore three epoxide functions, then crosslinking can take place during polymerization with monomer M. The thermosetting material can therefore be obtained in a single polymerization step, and monomer M also acts as the crosslinking agent in such a case.

[0088] When the monomer M is trivalent and the compound of formula (I) is divalent, the monomer M and the compound of formula (I) are introduced in a molar proportion (I):M ranging from 6:1 to 1:6, preferably ranging from 5:1 to 1:5, even more preferably from 4:1 to 1:4, typically about 3:1.

[0089] When the monomer M is divalent and the compound of formula (I) is divalent, the monomer M and the compound of formula (I) are introduced in a molar proportion (I):M ranging from 6:1 to 1:6, preferably ranging from 4:1 to 1:4, even more preferably from 3:1 to 1:2, typically about 2:1.

[0090] When the monomer M is divalent and the compound of formula (I) is trivalent, the monomer M and the compound of formula (I) are introduced in a molar proportion (I):M ranging from 6:1 to 1:6, preferably ranging from 2:1 to 1:2, even more preferably from 1.5:1 to 1:1.3, typically about 1.3:1.

[0091] When the monomer M is trivalent and the compound of formula (I) is trivalent, the monomer M and the compound of formula (I) are introduced in a molar proportion (I):M ranging from 6:1 to 1:6, preferably ranging from 4:1 to 1:4, even more preferably from 3:1 to 1:2, typically about 2:1.

[0092] Advantageously, the monomer M and the compound of formula (I) are introduced in a molar proportion equivalent to the reactive functions of monomer M as defined above, and epoxide functions of the compound of formula (I) (proportion abbreviated as MR:(I)R) ranging from 0.8:1 to 1:0.8, preferably from 0.9:1 to 1:0.9, typically about 11. The reaction can take place in an organic solvent, more preferentially polar, in a quantity by mass ranging from 0% by mass to 1000% by mass of the mass of the monomers involved, preferably ranging from 5% by mass to 500% by mass of the monomers involved, preferably still ranging from 10% by mass to 50% by mass of the monomers involved.

[0093] In the case where the solvent is a polar organic solvent, it is preferably aprotic, chosen by those skilled in the art as capable of solubilizing the monomer(s) and possibly the polymer produced, and with a sufficiently high boiling point to carry out the reaction under the required conditions, such as, for example, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, acetone, racetonitrile, trifluorotoluene, or diphenyl ether. When this solvent is miscible with water, the solvent may consist of a mixture of the aprotic solvent with water, for example, a dimethyl sulfoxide / water mixture.

[0094] The polymerization reaction can be carried out at a temperature ranging from 40 °C to 200 °C, preferably from 50 °C to 160 °C, preferably from 60 °C to 120 °C, more preferably from 70 °C to 100 °C, typically about 80 °C. The duration of the reaction can range from 10 minutes to 4 hours, typically about 60 minutes.

[0095] At the end of the process according to the invention, the polymer produced can be recovered in a known manner, stored where appropriate, and possibly processed for its subsequent uses by techniques known to those skilled in the art.

[0096] The polymer thus obtained can have a glass transition temperature (Tg) ranging from 10 °C to 50 °C, preferably from 20 °C to 35 °C. The Tg can be measured by any method known to those skilled in the art, in particular that described in the examples.

[0097] Another object of the invention relates to a polymer obtainable by the polymerization step of a compound of formula (I) as defined above. Optionally, the polymer has undergone the additional crosslinking step as defined above. Those skilled in the art can determine the structure of the polymer obtained based on the nature of the monomers M, the compounds of formula (I), and optionally the crosslinking agents used. This polymer is preferably a thermosetting material. The polymer advantageously has a glass transition temperature (Tg) ranging from 0°C to 200°C, preferably from 10°C to 200°C, preferably from 0°C to 50°C, typically from 20°C to 35°C.

[0098] Another object of the invention relates to the use of a compound of formula (I) as a precursor of polymeric materials, in particular thermosetting materials, or as an adhesive. It is understood that, in the context of use as an adhesive, the compound of formula (I) must be brought into contact with a crosslinking agent to obtain the desired effect.

[0099] The aforementioned features of the present invention, as well as others, will be better understood upon reading the following description of several illustrative and non-limiting embodiments of the invention. EXAMPLES

[0100] The following examples illustrate particular embodiments of the invention without limiting its scope.

[0101] The following abbreviations are used in the examples: - AHEW - amine hydrogen equivalent weight - d - diameter - DCM - dichloromethane - DCC - A,M-dicyclohexylcarbodiimide - DMAP - 4-dimethylaminopyridine - DMF - dimethylformamide - DMSO - dimethyl sulfoxide - DSC - Differential Scanning Calorimetry - EDC - A-(3-dimethylaminopropyl)-M-ethylcarbodiimide hydrochloride - HMBC - heteronuclear multiple-bond correlation - HSQC - heteronuclear single quantum coherence - 1 - length - MCPBA - metachloroperbenzoic acid - TA - ambient temperature - TMS - tetramethylsilane - THF - tetrahydrofuran - v / v - volume / volume 1. Materials and methods 1.1. Characterization of molecules

[0102] Structural analysis and determination of the molar purities of the synthetic molecules are performed by NMR analysis. The spectra are acquired on a Bruker Avance 3400 MHz spectrometer equipped with a BBFO-zgrad 5 mm broadband probe. The quantitative ¹H NMR experiment uses a single 30° pulse sequence and a 3-second repetition delay between each of the 64 acquisitions. The samples are solubilized in a deuterated solvent, deuterated chloroform (CDC13), unless otherwise specified. The deuterated solvent is also used for the lock signal. For example, calibration is performed on the proton signal of CDC13 deuterated at 7.20 ppm relative to a TMS reference at 0 ppm. The ¹H NMR spectrum coupled with the 2D HSQC ¹H / ¹³C and HMBC ¹H / ¹³C experiments allows the Structural determination of molecules. Molar quantifications are performed from the quantitative 1D 'H NMR spectrum.

[0103] The ERETIC quantification method consists of measuring the mass percentage of one or more species present in a sample by external calibration, using as a standard a reference tube of triphenyl phosphate (TPP) at 48.5 mmol / L in acetone-d6. A quantitative ¹H NMR spectrum with a single 30° pulse is recorded with a 62-second recycle time (RT) between each of the 16 scans. The sample to be analyzed is precisely weighed and dissolved in a precise volume of the deuterated solvent appropriate for the sample (approximately 10 mg / mL). A series of ¹H NMR spectra with a single 30° pulse, with the same number of scans (generally 8), the same general relativity (GR), and different RTs (generally 5 / 10 / 15, or even 20 seconds), are recorded and then superimposed to ensure the quantitative nature of the measurement. A 1H NMR spectrum with a single 30° pulse is then recorded on the same tube using the adapted DI (from the previous test) at 64 or 128 scans.The TPP signal is integrated onto the reference spectrum, which counts for 15 protons and is recorded as "Define as ERETIC reference". The most isolated and resolved signal(s) of each species identified on the sample spectrum are also integrated. Using the ERETIC (Calculate Concentration) module of Topspin, it is necessary to enter the precise volume of solvent used, the number of protons assigned to each of the integrated signals, and the molar mass of each species corresponding to the integrated signals. The concentration of the species in the sample is calculated directly by this module. This value is compared to the theoretical concentration (mmol / L) calculated using the sample weight, the solvent volume, and the molar masses of each species.

[0104] x ^'expected

[0105] with

[0106] C [ mnwl ] __ mIM * Expected! L 1 V

[0107] where m = weighed mass [mg]; M = molar mass [^7]; V = volume of solvent [l] 1.2. Chemical Compounds

[0108] All compounds are from commercial sources (Sigma-Aldrich and BLD Pharmatech).

[0109] 2. Synthesis of compound A (benzene-1,3,5-triyl tris(3-(oxiran-2-yl)propanoate)

[0110] The synthesis of compound A is carried out in two steps from phloroglucinol. 2.1. Synthesis of compound Al [yes] OH ..,¾ DCO DMAP OO J.A + HO"' yhF Ô HO' 'OH iMr U ;• Oh (A-1)

[0112] Under argon protection, a solution of phloroglucinol (3.00 g; 23.8 mmol) in anhydrous THF (150 mL) is cooled slightly to 10 °C. Then, the following are added in the specified order: 4-pentenoic acid (8.57 g; 86.0 mmol), DCC (15.46 g; 74.9 mmol), and finally DMAP (0.872 g; 7.14 mmol). The reaction mixture is stirred at 10–15 °C for 1 hour and then for another 12–14 hours at 22–24 °C. The precipitate is then filtered and washed with DCM (3 x 20 mL). The permeate is concentrated under reduced pressure (Tbain = 30 °C, 5 mbar) to yield a two-phase system consisting of a yellow-orange oil and a white solid (residual dicyclohexylurea). The product is isolated by silica column chromatography (1 = 28 cm, d = 4.5 cm) by eluting with a mixture of petroleum ether and ethyl acetate (v / v, 3:1).The fractions of interest are combined and concentrated under reduced pressure (Tbain = 40 °C, 4 mbar) to obtain a clear, colourless oil (5.794 g, 15.56 mmol). Yield: 65%, purity: 98% (H-NMR). Attribution RMN (CDC13)#:

[0113]

[0114] O II 2 4 [Tables 1 OX at 3^$ ù— / y=o 6 / vo > r ■y Nê ô 1H (ppm) ô 13C (ppm) 1 5.74-5.90 136.1 2 4.99-5.10 116.1

[0115] 3 2.38-2.46 28.7 4 2.58 33.5 5 / 170.7 6 / 151.1 7 6.75 112.7 2.2. Synthesis of compound A

[0116] ir i "T i " ...... OO MCPBA O O --, OCM ï O (A-1) To a solution of benzene-1,3,5-triyl tris(pent-4-enoate) (compound A-1; 5.794 g, 15.56 mmol) in DCM (150 mL), MCPBA (13.420 g; <77%) is added in portions over 20 minutes. The reaction mixture is stirred at 22–24 °C for 24 hours. The resulting precipitate is then filtered and washed through the filter using DCM (3 x 20 mL). The permeate is stirred with an aqueous solution of Na₂SO₃ (30 g in 120 mL of water) for 5 hours. After separation, the aqueous phase is extracted using DCM (2 x 30 mL). The collected organic phases are stirred with an aqueous solution of NaHCO₃ (30 g in 120 mL of water) for 5 hours. After separation, the aqueous phase is extracted using DCM (2 x 30 mL). The combined organic phases are washed with demineralized water (30 mL) and finally evaporated under reduced pressure (Tbain = 40 °C, 5 mbar) to produce a yellowish oil.The target product is isolated by silica column chromatography (1 = 30 cm, d = 4.5 cm) using a mixture of petroleum ether and ethyl acetate (v / v, 1:2). The fractions of interest are combined, concentrated under reduced pressure (Tbain = 40 °C, 10 mbar), and then dried under deep vacuum (TA, 14 h, 0.15 mbar). A clear oil (4.803 g, 11.42 mmol) is obtained. Yield: 73%. This product crystallizes slowly at room temperature to form a white solid with a melting point of 45.9 °C. The purity is 93% (H NMR). Attribution RMN (CDC13)#:

[0118] [Tables2 Nê ô 1H (ppm) ô 13C (ppm) 1 2.50 and 2.74 47.0 2 2.95-3.02 51.0 3 1.71-1.85 and 1.99-2.12 27.4 4 2.63 30.5 5 / 170.6 6 / 151.0 7 6.79 112.7

[0119] 3. Synthesis of compound B (benzene-1.3.5-trivl tris(9-(oxiran-2-yl)nonanoate) (B)

[0120] The synthesis of compound B is carried out in two steps from phloroglucinol. 3.1. Synthesis of compound Bl

[0121] o o (B-1)

[0122] Under argon protection. A solution of phloroglucinol (3.00 g; 23.8 mmol) in anhydrous THF (150 mL) is cooled slightly to 10 °C. Then, the following are added in the specified order: 10-undecenoic acid (15.78 g; 86.0 mmol), DCC (15.46 g; 74.9 mmol), and finally DMAP (0.872 g; 7.14 mmol). The reaction mixture is stirred at 10–15 °C for 1 hour and then for a further 12–14 hours at 22–24 °C. The precipitate is then filtered and washed through a filter with DCM (3 × 20 mL). The permeate is concentrated under reduced pressure (Tbain = 30 °C, 5 mbar) to yield a slightly yellowish solid. This material is dissolved in a mixture of pentane and ethyl acetate (75 mL; 20:1, v / v) and filtered through silica (1 = 5 cm) by eluting with 150 mL of the previously mentioned mixture. This procedure is repeated four

[0123] times in series. Finally, the permeate is concentrated under reduced pressure (Tbain = 40°C, 8 mbar) to produce a transparent oil. A colorless oil (8.59 g, 13.75 mmol) is obtained. Yield: 58%, purity mass: 94% (H-NMR). Attribution RMN (CDC13)#:

[0124] O

[0125] [tables3 / 172.3 12 / 152.2 13 6.75 113.7 3.2. Synthesis of compound B

[0126]

[0127] To a solution of benzene-1,3,5-triyl tris(undec-1O-enoate) (compound Bl; 5.00 g, 8.00 mmol) in DCM (100 mL), MCPBA (6.90 g, <77%) is added in portions over 10-12 minutes. The reaction mixture is stirred at 22-24 °C for 24 hours. The resulting precipitate is then filtered and washed through the filter with DCM (3 x 15 mL). The permeate is stirred with an aqueous solution of Na₂SO₃ (15 g in 100 mL). water) for 5 hours. After separation, the aqueous phase is extracted using DCM (30 mL). The combined organic phases are stirred with an aqueous solution of NaHCO3 (15 g in 100 mL of water) for 5 hours. After separation, the aqueous phase is extracted using DCM (30 mL). The combined organic phases are washed with demineralized water (30 mL) and finally evaporated under reduced pressure (Tbain = 40 °C, 5 mbar) to yield a yellowish oil. This crude product is solubilized in a mixture of pentane and ethyl acetate (20 mL, 3:1, v / v) and filtered through a silica gel layer (approx. 5 cm) by eluting with the previously mentioned mixture (50 mL). The permeate is then concentrated under reduced pressure (Tbain = 40°C, 7 mbar) to obtain a colorless oil (3.274 g, 4.87 mmol). Yield: 61%, mass purity: 94% (H-NMR). Attribution RMN (CDC13)#: O

[0129] [Tables4 Nê ô 'H (ppm) ô 13C (ppm) 1 2.40 and 2.68 46.4 2 2.84 51.2 3 1.46 31.5 4 1.39 24.6 5-8 1.25-1.35 28.1 9 1.65 23.8 10 2.46 33.3 11 / 171.1 12 / 151.1 13 6.75 112.0

[0130] 4. Synthesis of compound C (benzene- L3.5-trivl tris(7-oxabicyclo[4.l.01heptane-3- carboxylate))

[0131]

[0132] (C) The synthesis of compound C is carried out in two steps from phloroglucinol. 4.1, Synthesis of the compound Cl(benzene-L3.5-triyl tris(cyclohex-3-ene-l-carboxylate')') OH THF C°2H EDO, DMAP

[0133]

[0134] Under argon protection, a solution of phloroglucinol (4.00 g, 31.7 mmol) in anhydrous THF (200 mL) is cooled to 10 °C. Then, the following are added in the specified order: 3-cyclohexene-l-carboxylic acid (14.55 g, 113 mmol), EDC (21.67 g, 113 mmol), and finally DMAP (1.16 g, 9.5 mmol). The reaction mixture is stirred at 10–15 °C for 1 hour and then left overnight at room temperature. The precipitate is then filtered twice and washed with DCM (2 x 40 mL). The permeate is concentrated under reduced pressure (Tbain = 40 °C, 50 mbar) to yield a yellow oil. It is redissolved in DCM (130 mL) and washed with distilled water (5 x 130 mL) until the EDC adduct disappears. The organic phase is dried with Na2SO4 and concentrated under reduced pressure. A slightly yellowish solid (12.5 g, 23.0 mmol) is obtained. Yield 73%, mass purity: 83% (H-NMR), melting point: 66 °C. Attribution RMN (CDC13)#:

[0135] g

[0136] [Tables5 Nê ô 'H (ppm) ô 13C (ppm) 1 6.76 112.6 2 / 151.2 3 / 173.5 4 2.71 39.4 5 2.31 27.2 6 5.66 124.8 7 5.66 126.7 8 2.09 24.2 9 1.75 24.9 4.2. Synthesis of compound C

[0137] A solution of benzene-1,3,5-triyl-tris(cyclohex-3-ene-1-carboxylate) (compound Cl; 12.0 g, 22.1 mol) in DCM (250 mL) is cooled to 0 °C. After cooling, MCPBA (28.84 g, <77%) is added slowly so as not to exceed 10 °C in the medium. The reaction mixture is stirred at room temperature overnight. The resulting precipitate is then filtered and washed with DCM (2 x 50 mL). The permeate is stirred for 7 h with a 10% concentrated aqueous Na₂SO₃ solution (250 mL). After separation, the aqueous phase is extracted with DCM (2 x 60 mL). The organic phases are combined and stirred with an aqueous NaHCO₃ solution (60 g in 240 mL of water) overnight. After separation, the aqueous phase is extracted with DCM (2x60 mL).The combined organic phases are washed with distilled water (60 mL) and finally evaporated under reduced pressure (Tbain = 40°C, 5 mbar) to produce an oil that crystallizes slowly at room temperature. A white solid (11.5 g, 21.0 mmol) is obtained. Yield 95%, mass purity: 91% (H NMR), melting point: 118 °C.

[0138] According to NMR analysis, it is likely that the endo- and exo- forms which coexist generate close but distinct peaks. Attribution RMN (CDC13)#:

[0140] [Tablesô N2 ô 'H (ppm) ô 13C (ppm) 1 6.73 112.4 r 6.74 112.5 2 / 151.0 2' / 151.0 3 / 172.9 3' / 172.2 4 2.69 35.9 4' 2.43 37.4 5 2.02-2.33 26.9 5' 2.22-2.26 26.3 6 3.22 51.8 6' 3.16 50.5 7 3.13 51.2 7' 3.14 51.4 8 1.84-1.96 22.6 8' 1.79-2.21 23.2 9 1.48 22.6 9' 1.67 20.8 5. Synthesis of compound D (benzene-1.3.5-trivl tris(2-methyloxirane-2-carboxylate)

[0141]

[0142] The synthesis of compound D is carried out in two steps from phloroglucinol. 5.1. Synthesis of compound Dl (D-1)

[0144] The compound Dl (l,l',l"-(l,3,5-benzenetriyl) tris(2-methyl-2-propenoate) can be obtained according to the protocol described in US document 20200317870. Attribution RMN (CDC13)#:

[0146] [Tables7 Nê ô 'H (ppm) ô 13C (ppm) 1 7.09 114.2 2 / 151.6 3 / 125.3 4 / 135.4 5 5.92 and 6.29 128.7 6 2.01 18.4 5.2 Synthesis of compound D

[0147] To a solution of (l,l',l"-(l,3,5-benzenetriyl)tris(2-methyl-2-propenoate) (compound Dl; 3.00 g, 9.08 mmol) in DCM (100 mL), MCPBA (7.84 g, < 77%) is added in portions over 8-10 minutes. The reaction mixture is stirred at 22-24 °C for 24 hours. The resulting precipitate is then filtered and washed through the filter using DCM (2 x 10 mL). The permeate is stirred with an aqueous solution of Na₂SO₃ (10 g in 50 mL of water) for 5 hours. After separation, the aqueous phase is extracted using DCM (30 mL). The collected organic phases are stirred with an aqueous solution of NaHCO₃ (10 g in 50 mL of water) for 5 hours. After separation, the aqueous phase is extracted by The DCM (30 mL). The combined organic phases are washed with demineralized water (3 x 20 mL) and finally evaporated under reduced pressure (Tbain = 40 °C, 5 mbar) to yield a colorless oil (3.257 g; 8.61 mmol). Yield 95%, mass purity: greater than 75% (H NMR). Attribution RMN (CDC13)#:

[0148]

[0149] [Tables8 Nê ô 'H (ppm) ô 13C (ppm) 1 6.8 113.0 2 / 151.4 3 / 168.6 4 / 53.6 5 2.80 and 3.18 53.1 6 1.60 17.2 6. Evaluation of the properties of the compound (A)

[0150] The properties of compound (A) with respect to DGEBA were evaluated in thermosetting materials. Various amine derivatives (crosslinking agents) were combined with this new monomer to study its thermal properties in formulations and thus compare them to DGEBA-based formulations: • Priamine 1071 (pf < -30 °C, AHEW = 140 g / eq), • Urea (pf = 132-135 °C, AHEW = 15 g / eq).

[0151] The protocol for thermal properties in formulation was carried out as follows.

[0152] The monomer was weighed with the corresponding diamine (1 equivalent with respect to the reactive functions). The mixture was dissolved in a DMSO:water mixture (% mass = 74:26) at a mass concentration between 10 and 12%. After homogenization, the mixture was then placed in a vacuum oven (5 mbar) with a slight nitrogen flow at 120 °C for 60 to 100 minutes (preheating step). A portion of the material obtained after preheating was taken to continue the second part of the reaction in the DSC (aluminum crucible with Treaction < Tdecomposition), under helium at 40 mL / min at 80 or 210 °C for 60 minutes. The glass transition temperature (Tg) of the material obtained was then measured by DSC, under helium at 40 mL / min, according to the method: 1. Cooling from 25°C to -150°C at -50°C / min, 2. Isothermal temperature of -150 °C for 18 min. 3. Heating from -150 °C to +250 °C at 50 °C / min, 4. Isothermal at -150 °C for 18 min, 5. Heating from -150 °C to +250 °C at 50 °C / min.

[0153] The Tg was measured on the last heating ramp.

[0154] Several tests were carried out by varying the monomer used, the crosslinking agent (the diamine) used, and certain reaction conditions. These tests are summarized in the table below.

[0155] [Tables9] Test 1 2 3 4 Monomer Compound (A) according to the invention DGEBA Diamine Urea Priamine 107 1 Urea Priamine 107 1 molar equivalent diamine molecule: monomer 1:1.33 1:2 molar equivalent functional group (NH:epoxide) 1:1 1:1 Mass concentration of reactants (%) 9.6 12.44 12 12 Preheating time (min) 100 100 60 60 Preheating temperature (°C) 120 120 120 120 Reaction time (min) 60 60 60 60 Reaction temperature (°C) 80 80 210 210 Tg (°C) 33.97 21.32 29.80 23.59

[0156] The glass transition temperature of materials prepared from compound (A) compared to those prepared from DGEBA is similar, regardless of the crosslinking agent (Urea or Priamine 1071). These results demonstrate that the use of the monomers according to the invention makes it possible to obtain thermosetting materials with properties equivalent to those obtained with a reference monomer such as DGEBA, without the drawback of being derived from bisphenol A and epichlorohydrin, and thus having improved HSE properties.

Claims

1. Demands Compound of formula (I) in which: - Ri and R3 are identical and denote a group according to the following formula (II): (II) in which: - E represents a single bond or a C1-C12 hydrocarbon divalent group possibly comprising one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of group (II) to the rest of the compound of formula (I); R5 represents a group of formula (II) identical to Ri and R3 or -O-X4, with X4 representing a Ci-Ci8 alkyl, a C2-Cig alkenyl, a C6-Ci4 aryl, or a (C6-Ci4)aryl-(Ci-C6)alkyl, preferably R5 represents a group of formula (II) identical to Ri and R3; - R2, R4 and R6, identical or different, represent a hydrogen atom or an alkyl in C1-C24.

2. Compound according to claim 1, characterized in that R2, R4 and R6, identical or different, represent a hydrogen atom or a C1-C4 alkyl, preferably, R2, R4 and R6 represent a hydrogen atom.

3. Compound according to claim 1 or 2, characterized in that E represents a divalent hydrocarbon group in CrC4, typically in C2, or in C5-C10, typically in C8, optionally comprising one or more heteroatoms, preferably E represents an alkyl in CrC4, typically in C2, or in C5-C10, typically in C8, optionally comprising one or more heteroatoms.

4. A compound according to any one of claims 1 to 3, characterized in that Xb, X2 and X3, identical or different, represent a hydrogen atom or a Ci-C6 alkyl, preferably a hydrogen atom or a methyl, and / or Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4-C8 carbocycle, preferably a saturated C4-C8 carbocycle, advantageously a cyclopentane, a cyclohexane or a cycloheptane.

5. Compound according to any one of claims 1 to 4, selected from the group consisting of 0 X 0 J ,o 0 (A) (D)

6. A process for preparing a compound of formula (I) according to any one of claims 1 to 5, comprising a step b) of epoxidizing a compound of formula (1-2) in which: - Ri” and R3’ ’ are identical and designate a group according to the following formula (II-2): (11-2) in which: - E represents a single bond or a divalent hydrocarbon group in CrCi2 possibly including one or more heteroatoms; - Xi, X2 and X3, whether identical or different, represent a hydrogen atom, a Ci-C6 alkyl group or a C6-Ci4 aryl group, and / or - Xi and X3 or X2, or a carbon atom from the divalent hydrocarbon group of E and X3 or X2 can be linked together, with the carbon atoms of the epoxide group, to form a C4 to C8 carbocycle or a heterocycle having 5 to 8 links; - the symbol (*) represents the point of attachment of the group of formula (II-2) to the rest of the compound of formula (1-2); R5” denotes a group identical to Ri” and R3”, or -O-X4, with X4 representing a Ci-Ci8 alkyl, a C2-Cig alkenyl, a C6-Ci4 aryl or a (C6-Ci4)aryl-(Ci-C6)alkyl; R2, R4 and R6, identical or different, represent a hydrogen atom or a Ci-C^ alkyl, preferably a hydrogen atom or a CrCi2 alkyl, preferably a hydrogen atom or a Ci-C6 alkyl, preferably a hydrogen atom or a CrC4 alkyl, more preferably still a hydrogen atom.

7. A process according to claim 6, further comprising a step a) preceding step b), step a) being a step of bringing the following compounds into contact: - a compound with formula (1-1) (M) in which: - R / and R3' denote an -OH group, - R5' denotes a -OH or -O-X4 group, with X4 as defined in claim 6, and - R2, R4 and R6 are as defined in claim 6; with - a compound according to the following formula (II-l): X2 (H-1) in which: Y represents a group -OH, -ORa, or a halogen atom, with Representing an alkyl group in C1-C6, and E, Xi, X2 and X3 are as defined in claim 6.

8.

9. Use of a compound of formula (I) according to any one of claims 1 to 5 as a precursor of polymeric materials, in particular thermosetting materials, or as an adhesive. A process for preparing a thermosetting material comprising a step of polymerizing a compound of formula (I) according to any one of claims 1 to 5; optionally, the process further comprises a crosslinking step.

10. Thermosetting material that can be obtained by the process according to claim 9.